CN113950519B - Refrigerant-containing composition, use thereof, refrigerator having the same, and method for operating the refrigerator - Google Patents
Refrigerant-containing composition, use thereof, refrigerator having the same, and method for operating the refrigerator Download PDFInfo
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- CN113950519B CN113950519B CN202080043594.8A CN202080043594A CN113950519B CN 113950519 B CN113950519 B CN 113950519B CN 202080043594 A CN202080043594 A CN 202080043594A CN 113950519 B CN113950519 B CN 113950519B
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims description 12
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 claims abstract description 6
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010586 diagram Methods 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 23
- 239000010721 machine oil Substances 0.000 claims description 14
- 238000002485 combustion reaction Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 8
- 239000000700 radioactive tracer Substances 0.000 description 8
- -1 unsaturated fluorocarbon compound Chemical class 0.000 description 8
- 239000007850 fluorescent dye Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- YUCFVHQCAFKDQG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH] YUCFVHQCAFKDQG-UHFFFAOYSA-N 0.000 description 4
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 3
- 229920001774 Perfluoroether Polymers 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ORNGPPZBMMHKPM-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethane Chemical compound FC(F)(F)C(F)(F)OC(F)(F)C(F)(F)F ORNGPPZBMMHKPM-UHFFFAOYSA-N 0.000 description 1
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 1
- QZFIQARJCSJGEG-UHFFFAOYSA-N 1,1,1,2-tetrafluoro-2-(1,2,2,2-tetrafluoroethoxy)ethane Chemical compound FC(F)(F)C(F)OC(F)C(F)(F)F QZFIQARJCSJGEG-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 1
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- WSNAAHWRJMRVCU-UHFFFAOYSA-N 2-tert-butyl-3,4-dimethylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C WSNAAHWRJMRVCU-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- FKTCIVHJKSDNRI-UHFFFAOYSA-N 6-butyl-2,3-dimethylphenol Chemical group CCCCC1=CC=C(C)C(C)=C1O FKTCIVHJKSDNRI-UHFFFAOYSA-N 0.000 description 1
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- JRHMNRMPVRXNOS-UHFFFAOYSA-N trifluoro(methoxy)methane Chemical compound COC(F)(F)F JRHMNRMPVRXNOS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B13/00—Compression machines, plants or systems, with reversible cycle
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
- F25B2400/12—Inflammable refrigerants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Liquid Developers In Electrophotography (AREA)
Abstract
The invention aims to provide a novel mixed refrigerant with low GWP. As a solution, a composition containing a refrigerant comprising trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123) and trans-1, 3-tetrafluoropropene (R1234 ze (E)) is provided.
Description
Technical Field
The present invention relates to a refrigerant-containing composition, use thereof, and a refrigerator having the same, and a method for operating the refrigerator.
Background
R410A is currently used as an air conditioning refrigerant for home air conditioning and the like. R410A is a 2-component mixed refrigerant of difluoromethane (CH 2F2; HFC-32 or R32) and pentafluoroethane (C 2HF5; HFC-125 or R125) is an azeotrope-like composition.
However, R32 having GWP 675 is used more often because the Global Warming Potential (GWP) of R410A is 2088 and there is an increased concern about global warming.
Accordingly, various low GWP mixed refrigerants capable of replacing R410A have been proposed (patent document 1).
Prior art literature
Patent literature
Patent document 1: international publication No. 2015/141678
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a novel low GWP mixed refrigerant.
Means for solving the problems
Item 1.
A refrigerant-containing composition, wherein:
The above refrigerant contains trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and trans-1, 3-tetrafluoropropene (R1234 ze (E)).
Item 2.
The composition of item 1, wherein:
In the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the pattern surrounded by or on the lines AA1, A1B, BD, DR, RC, CO and OA respectively connecting the following 7 points (excluding the points on the lines BD, CO and OA),
Point A (76.2,0.0,23.8),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0),
Lines AA1, A1B, BD, CO and OA are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
Item 3.
The composition of item 1, wherein:
in the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the pattern surrounded by the lines GG1, G1A1, A1B, BD, DR, RC and CG respectively connecting the following 7 points or on the lines (wherein the points on the lines BD and CG are not included),
Point G (72.0,28.0,0.0),
Point G1 (72.0,3.3,24.7),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines GG1, G1A1, A1B, BD and CG are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
Item 4.
The composition of item 1, wherein:
In the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the figure defined by the lines JQ, QN, NM, MA, A1B, BD, DR, RC and CJ, respectively, connecting the following 9 points or on the lines (excluding the points on the lines BD and CJ),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QN, NM, MA1, A1B, BD and CJ are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
Item 5.
The composition of item 1, wherein:
in the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the pattern enclosed by or on the lines JQ, QR, RC and CJ respectively connecting the following 4 points (excluding the points on the line CJ),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QR and CJ are straight lines,
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
Item 6.
The composition of item 1, wherein:
In the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of or on the graph surrounded by lines SN, NM, MA1, A1B, BF, FS1 and S1S each connecting 7 points below,
Point S (64.6,26.0,9.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point F (0.0,71.7,28.3)
At point S1 (26.8,54.4,18.8),
Lines SN, NM, MA1, A1B and BF are straight lines,
Line FS1 is denoted as (x, 0.0041x 2-0.7562x+71.7,-0.0041x2 -0.2438x+28.3),
Line S1S is denoted (x, 0.00155x 2-0.8939x+77.236,-0.00155x2 -0.1061x+22.764).
Item 7.
The composition of item 1, wherein:
In the above refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the figure defined by straight lines P 'Q, QQ and Q1P' connecting the following 3 points, respectively, or on the above lines,
Point P (55.4,42.7,1.9),
Point Q (62.1,34.5,3.4)
Point Q1 (52.8,43.5,3.7).
Item 8.
The composition of item 1, wherein:
also contains 2, 3-tetrafluoro-1-propene (R1234 yf).
Item 9.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are within a range of a graph enclosed by straight lines ArA1r、A1rBr、BrDr、DrRr、RrC、CO and OA r connecting the following 7 points, respectively, or on the above lines (wherein, the points on lines B rDr, CO r and OA are not included) in the point diagram in which the sum of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the sum of R1234yf is 100 mass% is the vertex,
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Point R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0).
Item 10.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are defined as the vertices at the point where HFO-1132 (E) is 100 mass%, the point where HFO-1123 is 100 mass%, and the point where the sum of R1234ze (E) and R1234yf is 100 mass%, respectively:
When 0.53. Gtoreq.r > 0, in the range of the pattern enclosed by straight lines GG1、G1rA1r、A1rBr、BrDr、DrRr、RrC and CG connecting the 7 points below, respectively, or on the above lines (wherein, points on lines B rDr and CG are not included,
Point G (72.0,28.0,0.0),
Points G r(72.0,1.7734r2 +4.5133r+24.7, 28.0-y),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0),
When 1.0 > r > 0.53, the image is within the range of the figure enclosed by straight lines GI、IAr、ArA1r、A1rBr、BrDr、DrRr、RrC and CG connecting the following 8 points respectively or on the above lines (wherein, the points on lines IA r、BrDr and CG are not included),
Point G (72.0,28.0,0.0),
Point I (72.0,0.0,28.0),
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
Item 11.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are within a range of a graph enclosed by straight lines JQr、QrNr、NrMr、MrA1r、A1rBr、BrDr、DrRr、RrC and CJ connecting the following 9 points, respectively, or on the above-mentioned lines (wherein, the points on the lines BD and CJ are not included) in the point of 100 mass% HFO-1132 (E), the point of 100 mass% HFO-1123, and the point of 100 mass% of R1234ze (E) and the point of R1234yf, respectively,
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
Item 12.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), in a 3-component composition diagram in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of the sum of R1234ze (E) and R1234yf is 100 mass% are vertices, the coordinates (x, y, z') are within a range of a graph enclosed by straight lines JQ r、QrRr、Rr C and CJ, which connect the following 4 points, respectively, or on the above-mentioned lines (excluding the points on CJ),
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
Item 13.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are within a range of a graph enclosed by straight lines SrNr、NrMr、MrA1r、A1rBr、BrFr、FrS1r and S rSr connecting the following 7 points, respectively, or on the above-mentioned line (excluding the point on the line B rFr), the points of HFO-1132 (E) being 100 mass%, the points of HFO-1123 being 100 mass%, the points of R1234ze (E) and R1234yf being 100 mass%, respectively,
Point S r(1.4r2+1.3r+64.6,-0.8r2 -4.0r+26.0, 100.0-x-y),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point F r(0.0,-2.6r2 -7.3r+71.7, 100.0-y) and
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8).
Item 14.
The composition of item 1, wherein:
Also contains R1234yf,
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are within the range of or on the line defined by straight lines P rQr、QrQ1r and Q1 rPr connecting the following 3 points, respectively, in a 3-component composition diagram in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of R1234ze (E) and R1234yf are 100 mass%, respectively,
Point P r(-0.2r2-0.5r+55.4,100.0-x-z,0.6r2 +0.7r+1.9),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y) and
Point Q r(-2.4r2-0.8r+52.8,100.0-x-z,3.6r2 +0.8r+3.7).
Item 15.
The composition of any one of claims 1-14, wherein: the composition is used as a working fluid for a refrigerator.
Item 16.
The composition of any one of claims 1 to 15 for use as a replacement refrigerant for R410A.
Item 17.
Use of the composition of any one of items 1 to 15 as a replacement refrigerant for R410A.
Item 18.
A refrigerator containing the composition of any one of claims 1 to 15 as a working fluid.
Item 19.
A method of operating a refrigerator, comprising:
a step of circulating the composition according to any one of claims 1 to 15 as a working fluid in a refrigerator.
Effects of the invention
The refrigerant of the present invention can be used as a novel low GWP mixed refrigerant.
Drawings
FIG. 1 is a schematic view of an apparatus used in the combustibility test.
Fig. 2 is a diagram showing a graph defining the refrigerant of the present invention in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%.
Fig. 3 is a diagram showing a graph of a refrigerant in which the ratio R of R1234yf is 0.5, which is a refrigerant in which the present invention is specified in a 3-component composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and HFO-1234yf is 100 mass%, that is, in which the total of R1234yf and R1234ze (E) is 1.
Fig. 4 is a diagram showing a graph of a refrigerant in which the ratio R of R1234yf is 0.593, which is a refrigerant in which the present invention is specified in a 3-component composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and HFO-1234yf is 100 mass%, that is, in which the total of R1234yf and R1234ze (E) is 1.
Fig. 5 is a diagram showing a graph of a refrigerant in which the ratio R of R1234yf is 1, which is a refrigerant of the present invention defined in a 3-component composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and HFO-1234yf is 100 mass%, that is, the total of R1234yf and R1234ze (E) is 1.
Fig. 6 is a diagram showing a graph of a refrigerant in which the ratio R of R1234yf is 0, 0.5, 0.593, and 1, in a 3-component composition diagram in which the total of R1234yf and R1234ze (E) is 100 mass%, which is a refrigerant according to the present invention, is defined as 1.
Detailed Description
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a mixed refrigerant containing trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and trans-1, 3-tetrafluoro-1-propene (R1234 ze (E)) has the above characteristics.
The present invention was based on the findings described above, and results of further repeated studies were obtained. The present invention includes the following embodiments.
Definitions of the terms >
In the present specification, the term "refrigerant" includes at least a compound specified in ISO817 (international organization for standardization) and having a refrigerant number (ASHRAE number) starting with R indicating the type of refrigerant, and also includes a compound having the same characteristics as a refrigerant as the compound to which the refrigerant number has not been given. From the structural aspect of the compound, the refrigerant is broadly classified into "fluorocarbon-based compound" and "non-fluorocarbon-based compound". The "fluorocarbon-based compound" includes chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and Hydrofluorocarbons (HFCs). Examples of the "non-fluorinated hydrocarbon compound" include propane (R290), propylene (R1270), butane (R600), isobutane (R600 a), carbon dioxide (R744), and ammonia (R717).
In the present specification, the term "refrigerant-containing composition" includes at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) A composition which also contains other components and can be used to obtain a working fluid for a refrigerator by mixing with at least refrigerator oil; (3) working fluid for refrigerator containing refrigerator oil. In the present description, the composition of (2) is labeled as "refrigerant composition" differently from the refrigerant itself (including a mixture of refrigerants). The working fluid for a refrigerator of (3) is labeled "working fluid containing refrigerating machine oil" as distinguished from "refrigerant composition".
In the present specification, the term "replacement" refers to a case where the first refrigerant is replaced with the second refrigerant, and as the first type, means that the second refrigerant can be used to perform operation under optimal conditions by changing and adjusting the equipment as required only by a small part (at least one of the other parts such as refrigerator oil, gasket, expansion valve, and dryer) in the equipment designed to perform operation using the first refrigerant. That is, this type refers to the "replacement" of refrigerant to operate the same equipment. As a mode of "replacement" of this type, a "simple (drop in) replacement", "approximately simple (nealy drop in) replacement", and "update" may be performed in order from small to large, depending on the degree to which the replacement is required and the adjustment is performed when the replacement is performed with the second refrigerant.
As a second type, a case where equipment designed for operation using the second refrigerant is used for the same purpose as the existing use of the first refrigerant, and the second refrigerant is mounted for use is also included in the term "substitution". This type refers to the same purpose provided after "replacement" of the refrigerant.
In the present specification, the term "refrigerator" refers to all devices that take heat from an object or space to a temperature lower than the surrounding outside air and maintain the low temperature. In other words, the refrigerator is a conversion device that obtains energy from the outside to operate and converts the energy so as to move heat from a lower temperature side to a higher temperature side.
In this specification, the term "WCF micro-ignition" means that the combustion rate of the refrigerant is 10cm/s or less according to the American ANSI/ASHRAE34-2013 standard, which is the most readily combustible composition (the most disadvantageous component of flammability; worst case of formulation for flammability; WCF). In the present specification, the term "micro-ignition of refrigerant" means that the combustion rate of WCF is 10cm/s or less and the combustion rate of the most easily combustible fraction (the most adverse fraction component of combustibility; worst case of fractionation for flammability; WCFF) determined by the storage, transportation and leakage test at the time of use based on ANSI/ASHRAE34-2013 using WCF is 10cm/s or less, and it is determined that the combustion rate of ANSI/ASHRAE34-2013 standard is classified as "grade 2L".
In the present specification, the temperature slip (Temperature Glide) refers to an absolute value of a difference between a start temperature and an end temperature of a phase change process of a composition containing the refrigerant of the present invention in a heat exchanger of a refrigerant system.
1. Refrigerant and method for producing the same
1.1 Refrigerant composition
The refrigerant of the present invention is a mixed refrigerant containing trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and trans-1, 3-tetrafluoropropene (R1234 ze (E)).
The refrigerant of the present invention has a low GWP.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total amount thereof is represented by x, y and z, respectively, in the 3-component composition diagram in which the total amount of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern surrounded by or on the lines AA1, A1B, BD, DR, RC, CO and OA which connect the points 7 below, respectively (the points on the lines BD, CO and OA are not included),
Point A (76.2,0.0,23.8),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0),
Lines AA1, A1B, BD, CO and OA are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511). When the above condition is satisfied, the refrigerant of the present invention has a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of or on the graph surrounded by lines GG1, G1A1, A1B, BD, DR, RC and CG, respectively, which connect 7 points below (excluding points on lines BD and CG),
Point G (72.0,28.0,0.0),
Point G1 (72.0,3.3,24.7),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines GG1, G1A1, A1B, BD and CG are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511). When the above conditions are satisfied, the refrigerant of the present invention exhibits WCF microcombustibility (combustion rate of WCF composition is 10cm/s or less) in accordance with ASHRAE standards, while having a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total amount thereof is represented by x, y and z, respectively, in the 3-component composition diagram in which the total amount of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern defined by or on the lines JQ, QN, NM, MA, A1B, BD, DR, RC and CJ, respectively, which connect the following 9 points (excluding the points on the lines BD and CJ),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QN, NM, MA1, A1B, BD and CJ are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511). When the above conditions are satisfied, the refrigerant of the present invention exhibits microcombustibility (2L-class (combustion rate of WCF composition and WCFF composition: 10cm/s or less)) in accordance with ASHRAE standards, in addition to a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the pattern surrounded by or on the lines JQ, QR, RC and CJ respectively connecting the following 4 points (excluding the points on the lines CJ),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QR and CJ are straight lines,
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511). When the above condition is satisfied, the refrigerant of the present invention has a refrigerating capacity ratio of 85% or more based on R410A, a COP ratio of 92.5% or more based on R410A, and a condensation temperature slip of 1 ℃.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total amount thereof is represented by x, y and z, respectively, in the 3-component composition diagram in which the total amount of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of or on the pattern surrounded by lines SN, NM, MA1, A1B, BF, FS1 and S1S each connecting 7 points below,
Point S (64.6,26.0,9.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point F (0.0,71.7,28.3)
At point S1 (26.8,54.4,18.8),
Lines SN, NM, MA1, A1B and BF are straight lines,
Line FS1 is denoted as (x, 0.0041x 2-0.7562x+71.7,-0.0041x2 -0.2438x+28.3),
Line S1S is denoted (x, 0.00155x 2-0.8939x+77.236,-0.00155x2 -0.1061x+22.764). When the above condition is satisfied, the refrigerant of the present invention has not only a refrigerating capacity ratio of 85% or more based on R410A, but also a COP ratio of 95% or more based on R410A, and a discharge pressure ratio of 102% or less based on R410A.
In the refrigerant of the present invention, when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total amount of them is represented by x, y and z, respectively, in the 3-component composition diagram in which the total amount of HFO-1132 (E), HFO-1123 and R1234ze (E) is represented by 100 mass%, the coordinates (x, y, z) are within the range of the figure defined by straight lines P 'Q, QQ and Q1P' connecting the following 3 points, respectively, or on the lines,
Point P (55.4,42.7,1.9),
Point Q (62.1,34.5,3.4)
Point Q1 (52.8,43.5,3.7). When the above conditions are satisfied, the refrigerant of the present invention has a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 95% or more based on R410A, and a condensation temperature slip of 1 ℃.
The refrigerant of the present invention may further contain 2, 3-tetrafluoro-1-propene (R1234 yf).
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has a composition diagram of 3 components in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the points of HFO-1132 (E) and HFO-1123 are 100 mass%, the points of R1234ze (E) and R1234yf are 100 mass%, the coordinates (x, y, z') are on a line or a line (35B ) that is included in a graph of straight lines ArA1r、A1rBr、BrDr、DrRr、RrC、CO and OA r connecting 7 points below, respectively,
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Point R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0). When the above condition is satisfied, the refrigerant of the present invention has a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has the coordinates (x, y, z ') in a 3-component composition diagram having, as vertices, the point of HFO-1132 (E) being 100 mass%, the point of HFO-1123 being 100 mass%, the point of R1234ze (E) being 100 mass%, the point of R1234yf being 100 mass%, the sum of HFO-1123 being y, the sum of R1234ze (E) and R1234yf being z', and the ratio of R1234yf being R (0 < R < 1) when the sum of R1234yf and R1234yf being 1, in the 3-component composition diagram having, as vertices, the point of HFO-1132 (E) being 100 mass%, the point of HFO-1123 being 100 mass%, the sum of R1234ze (E) and R1234 yf:
When 0.53 is larger than or equal to r >0, the image is within the range of the graph enclosed by straight lines GG1、G1rA1r、A1rBr、BrDr、DrRr、RrC and CG respectively connecting the following 7 points or on the lines (wherein, the points on the lines B rDr and CG are not included),
Point G (72.0,28.0,0.0),
Points G r(72.0,1.7734r2 +4.5133r+24.7, 28.0-y),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0),
When 1.0 > r > 0.53, the image is within the range of the figure enclosed by straight lines GI、IAr、ArA1r、A1rBr、BrDr、DrRr、RrC and CG connecting the following 8 points respectively or on the above lines (wherein, the points on lines IA r、BrDr and CG are not included),
Point G (72.0,28.0,0.0),
Point I (72.0,0.0,28.0),
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0). When the above conditions are satisfied, the refrigerant of the present invention exhibits WCF microcombustibility (combustion rate of WCF composition is 10cm/s or less) in accordance with ASHRAE standards, while having a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has a composition map of 3 components in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the points of HFO-1132 (E) and HFO-1123 are 100 mass%, the points of R1234ze (E) and R1234yf are 100 mass%, the coordinates (x, y, z') are located in a range on a graph or a graph including straight lines JQr、QrNr、NrMr、MrA1r、A1rBr、BrDr、DrRr、RrC and CJ each connecting the following 9 points, or in which the points are not included,
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0). When the above conditions are satisfied, the refrigerant of the present invention exhibits microcombustibility (2L-class (combustion rate of WCF composition and WCFF composition: 10cm/s or less)) in accordance with ASHRAE standards, in addition to a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A.
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has a composition map of 3 components in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are in a range of or on a graph including straight lines JQ r、QrRr、Rr C and CJ, which are respectively connected to the following 4 points, in a composition map in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of R1234ze (E) and R1234yf are taken as vertices,
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0). When the above conditions are satisfied, the refrigerant of the present invention exhibits microcombustibility (2L grade (combustion speed of WCF composition and WCFF composition is 10cm/s or less)) in accordance with ASHRAE standards, as well as a freezing capacity ratio of 85% or more based on R410A and a COP ratio of 92.5% or more based on R410A, and a condensing temperature slip of 1 ℃ or less.
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has a composition diagram of 3 components in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the points of HFO-1132 (E) and HFO-1123 are 100 mass%, the points of R1234ze (E) and R1234yf are 100 mass%, the coordinates (x, y, z') are located on a line SrNr、NrMr、MrA1r、A1rBr、BrFr、FrS1r connecting 7 points below and a line of S1 rSr, respectively, or on a line (including a point of the above-mentioned line) and a point of 53B,
Point S r(1.4r2+1.3r+64.6,-0.8r2 -4.0r+26.0, 100.0-x-y),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point F r(0.0,-2.6r2 -7.3r+71.7, 100.0-y) and
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8). When the above conditions are satisfied, the refrigerant of the present invention exhibits microcombustibility (2L-stage (combustion speed of WCF composition and WCFF composition is 10cm/s or less)) in accordance with ASHRAE standards, in addition to a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 95% or more based on R410A, and a discharge pressure ratio of 102% or less based on R410A.
In the case where R1234yf is further contained, the refrigerant of the present invention preferably has a composition diagram of 3 components in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R (0 < R < 1), the coordinates (x, y, z') are in the range of the straight lines P rQr、QrQ1r and Q rPr connecting the following 3 points, respectively, or the graph is defined as the above-mentioned graph, in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of R1234ze (E) and the point of R1234yf are 100 mass%,
Point P r(-0.2r2-0.5r+55.4,100.0-x-z,0.6r2 +0.7r+1.9),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y) and
Point Q r(-2.4r2-0.8r+52.8,100.0-x-z,3.6r2 +0.8r+3.7). When the above conditions are satisfied, the refrigerant of the present invention exhibits microcombustibility (2L-stage (combustion speed of WCF composition and WCFF composition is 10cm/s or less)) according to ASHRAE standards, in addition to a refrigerating capacity ratio of 85% or more based on R410A and a COP ratio of 95% or more based on R410A, and a condensation temperature slip of 1 ℃ or less.
In all of the above embodiments, the refrigerant of the present invention may contain R1234ze (E) in an amount of more than 0 mass%, may contain 0.5 mass% or more, may contain 1 mass% or more, may contain 3 mass% or more, may contain 10 mass% or more, or may contain 15 mass% or more, relative to the entire refrigerant.
In all of the above embodiments, the refrigerant of the present invention may contain R1234yf in an amount of more than 0 mass%, may contain 0.5 mass% or more, may contain 1 mass% or more, may contain 3 mass% or more, may contain 10 mass% or more, or may contain 15 mass% or more, relative to the entire refrigerant.
In all of the above embodiments, the refrigerant of the present invention may contain R1234yf in an amount of more than 0% by mass and not more than 0.5% by mass, relative to the entire refrigerant.
In all of the above embodiments, the refrigerant of the present invention may contain 1 mass% or more, 3 mass% or more, 10 mass% or more, or 15 mass% or more of the total of R1234ze (E) and R1234yf with respect to the entire refrigerant.
The refrigerant of the present invention may contain not only HFO-1132 (E), HFO-1123, R1234ze (E) and R1234yf, but also other additional refrigerants within a range that does not impair the above-described characteristics and effects. In this respect, the refrigerant of the present invention preferably contains 99.5 mass% or more, more preferably 99.75 mass% or more, still more preferably 99.9 mass% or more, still more preferably 99.99 mass% or more, and most preferably 99.999 mass% or more of the total of HFO-1132 (E), HFO-1123, R1234ze (E) and R1234yf relative to the entire refrigerant.
In addition, the refrigerant of the present invention may be composed of only HFO-1132 (E), HFO-1123, R1234ze (E) and R1234 yf.
The additional refrigerant is not particularly limited, and can be widely selected. The mixed refrigerant may be contained in one kind alone or in two or more kinds as an additional refrigerant.
1.2 Use
The refrigerant of the present invention can be preferably used as a working fluid in a refrigerator.
The refrigerant of the present invention is suitable for use as a substitute refrigerant for R410A.
2. Refrigerant composition
The refrigerant composition of the present invention contains at least the refrigerant of the present invention and can be used for the same purpose as the refrigerant of the present invention. The refrigerant composition of the present invention can be mixed with at least a refrigerator oil to obtain a working fluid for a refrigerator.
The refrigerant composition of the present invention contains at least one component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may further contain at least one of the following other components, if necessary. As described above, when the refrigerant composition of the present invention is used as a working fluid in a refrigerator, it is usually used in combination with at least a refrigerator oil. Therefore, the refrigerant composition of the present invention is preferably substantially free of refrigerator oil. Specifically, in the refrigerant composition of the present invention, the content of the refrigerating machine oil is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, relative to the entire refrigerant composition.
2.1 Water
The refrigerant composition of the present invention may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1 mass% or less relative to the total amount of the refrigerant. By containing a small amount of water in the refrigerant composition, the intramolecular double bond of the unsaturated fluorocarbon compound that can be contained in the refrigerant is stabilized, and oxidation of the unsaturated fluorocarbon compound becomes difficult to occur, so that the stability of the refrigerant composition is improved.
2.2 Tracers
The tracer is added to the refrigerant composition of the present invention in a concentration that can be detected in such a way that the change can be traced when the refrigerant composition of the present invention is diluted, contaminated, or otherwise variously changed.
The refrigerant composition of the present invention may contain one kind of the tracer alone or two or more kinds of the tracer.
The tracer is not particularly limited, and may be appropriately selected from commonly used tracers.
Examples of the tracer include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorohydrocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorohydrocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N 2 O). As the tracer, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorohydrocarbons and fluoroethers are particularly preferred.
As the tracer, the following compounds are preferable.
FC-14 (tetrafluoromethane, CF 4)
HCC-40 (chloromethane, CH 3 Cl)
HFC-23 (trifluoromethane, CHF 3)
HFC-41 (fluoromethane, CH 3 Cl)
HFC-125 (pentafluoroethane, CF 3CHF2)
HFC-134a (1, 2-tetrafluoroethane, CF 3CH2 F)
HFC-134 (1, 2-tetrafluoroethane, CHF 2CHF2)
HFC-143a (1, 1-trifluoroethane, CF 3CH3)
HFC-143 (1, 2-trifluoroethane, CHF 2CH2 F)
HFC-152a (1, 1-difluoroethane, CHF 2CH3)
HFC-152 (1, 2-difluoroethane, CH 2FCH2 F)
HFC-161 (fluoroethane, CH 3CH2 F)
HFC-245fa (1, 3-pentafluoropropane) CF 3CH2CHF2) HFC-236fa (1, 3-hexafluoropropane) CF 3CH2CF3) HFC-236ea (1, 2, 3-hexafluoropropane) CF 3CHFCHF2) HFC-227ea (1, 2, 3-heptafluoropropane, CF 3CHFCF3) HCFC-22 (chlorodifluoromethane, CHClF 2)
HCFC-31 (chlorofluoromethane, CH 2 ClF)
CFC-1113 (chlorotrifluoroethylene, CF 2 =cclf)
HFE-125 (trifluoromethyl-difluoromethyl ether, CF 3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF 3OCH2 F) HFE-143a (trifluoromethyl-methyl ether, CF 3OCH3)
HFE-227ea (trifluoromethyl-tetrafluoro ethyl ether, CF 3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoro ethyl ether, CF 3OCH2CF3)
The refrigerant composition of the present invention may contain the tracer in total in an amount of about 10 parts by weight (ppm) to about 1000ppm with respect to the entire refrigerant composition. The refrigerant composition of the present invention may preferably contain the total amount of the tracers from about 30ppm to about 500ppm, more preferably from about 50ppm to about 300ppm, relative to the total amount of the refrigerant composition.
2.3 Ultraviolet fluorescent dyes
The refrigerant composition of the present invention may contain one kind of ultraviolet fluorescent dye alone or two or more kinds of ultraviolet fluorescent dye.
The ultraviolet fluorescent dye is not particularly limited, and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
Examples of the ultraviolet fluorescent dye include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, benzoxanthene, fluorescein, and derivatives thereof. As the ultraviolet fluorescent dye, either one or both of naphthalimide and coumarin are particularly preferable.
2.4 Stabilizers
The refrigerant composition of the present invention may contain one kind of stabilizer alone or two or more kinds of stabilizer.
The stabilizer is not particularly limited, and may be appropriately selected from commonly used stabilizers.
Examples of the stabilizer include nitro compounds, ethers, amines, and the like.
Examples of the nitro compound include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
Examples of the ethers include 1, 4-dioxane.
Examples of the amines include 2, 3-pentafluoropropylamine and diphenylamine.
In addition, butylhydroxyxylene, benzotriazole, and the like can be cited.
The content of the stabilizer is not particularly limited, but is preferably 0.01 to 5% by mass, and more preferably 0.05 to 2% by mass, based on the entire refrigerant.
2.5 Polymerization inhibitor
The refrigerant composition of the present invention may contain one kind of polymerization inhibitor alone or two or more kinds of polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and may be appropriately selected from commonly used polymerization inhibitors.
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone monomethyl ether, dimethyl-t-butylphenol, 2, 6-di-t-butyl-p-cresol, benzotriazole, and the like.
The content of the polymerization inhibitor is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, based on the entire refrigerant.
3. Working fluid containing refrigerator oil
The working fluid containing a refrigerating machine oil according to the present invention contains at least the refrigerant or the refrigerant composition according to the present invention and the refrigerating machine oil, and is used as a working fluid in a refrigerator. Specifically, the working fluid containing the refrigerating machine oil according to the present invention can be obtained by mixing the refrigerating machine oil used in the compressor of the refrigerator with a refrigerant or a refrigerant composition. In the working fluid containing the refrigerator oil, the refrigerator oil generally contains 10 to 50% by mass.
3.1 Refrigerator oil
The working fluid containing a refrigerating machine oil according to the present invention may contain one kind of refrigerating machine oil alone or two or more kinds of refrigerating machine oil.
The refrigerating machine oil is not particularly limited, and can be appropriately selected from commonly used refrigerating machine oils. In this case, more excellent refrigerating machine oil can be appropriately selected from the viewpoints of, for example, improving the compatibility (miscibility) with the mixture and the effect of the mixture on stability and the like, if necessary.
As the base oil of the refrigerator oil, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE), for example, is preferable.
The refrigerator oil may contain additives in addition to the base oil. The additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents and defoamers.
As the refrigerating machine oil, a kinematic viscosity at 40℃of 5 to 400cSt is preferable from the viewpoint of lubrication.
The working fluid containing a refrigerator oil of the present invention may contain at least one additive as required. Examples of the additives include the following compatibilizers.
3.2 Compatibilizer
The working fluid containing the refrigerator oil of the present invention may contain one kind or two or more kinds of the compatibilizer.
The compatibilizer is not particularly limited, and can be appropriately selected from commonly used compatibilizers.
Examples of the compatibilizer include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluoroethers, and 1, 1-trifluoroalkanes. As the compatibilizer, polyoxyalkylene glycol ether is particularly preferable.
4. Method for operating refrigerator
The method of operating a refrigerator according to the present invention is a method of operating a refrigerator using the refrigerant according to the present invention.
Specifically, the method for operating a refrigerator according to the present invention includes a step of circulating the refrigerant according to the present invention in the refrigerator.
The embodiments are described above, but it should be understood that: various modifications can be made to the embodiments and contents without departing from the gist and scope of the claims.
Examples
Hereinafter, examples will be described in more detail. The invention is not limited to these embodiments.
As described below, R410A (r32=50%/r125=50%) and the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), and the mixed refrigerant of HFO-1132 (E), HFO-1123, R1234ze (E) and R1234yf were evaluated, respectively.
For each mixed refrigerant, the burn rate was measured as WCF concentration in terms of the ANSI/ASHRAE 34-2013 standard with the mixed composition. The combustion rate is "2L-grade (micro-combustibility)", when it is 10cm/s or less.
The combustion speed test was performed as follows using the apparatus shown in fig. 1. First, the mixed refrigerant used was set to a purity of 99.5% or more, and the cycle of freezing, pumping and thawing was repeated until no trace of air was seen on the vacuum gauge, thereby performing deaeration. The combustion speed was measured by the closed method. The initial temperature is ambient temperature. Ignition is performed by generating an electric spark between the electrodes at the center of the sample chamber. The duration of the discharge is 1.0 to 9.9ms and the ignition energy is typically about 0.1 to 1.0J. The state of flame propagation is visualized by a schlieren method. A cylindrical container (inner diameter: 155mm, length: 198 mm) having 2 acrylic windows through which light was transmitted was used as a sample chamber, and a xenon lamp was used as a light source. The schlieren image of the flame was recorded with a high-speed digital video camera at 600fps frame rate 600 and saved in the PC.
The combustion speed (Su (cm/s)) is expressed by the volume of unburned gas consumed per unit time by the flame surface per unit area, and is calculated by the following formula.
Su＝Sb*ρu/ρb
Ρu; adiabatic flame temperature (unburned)
Ρb; adiabatic flame temperature (burnt)
Here, sb is obtained from a schlieren video image, ρu is a measured temperature, and ρb is calculated from the combustion heat and the constant pressure specific heat of the combustion gas.
The results of the combustion rate tests for the mixed refrigerants HFO-1132 (E), HFO-1123 and R1234ze (E) are shown in tables 1 and 2.
TABLE 1
TABLE 2
Based on these results, it was judged that: assuming that mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in the 3-component composition diagram of FIG. 2 in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, a mixed refrigerant having a composition with coordinates (x, y, z) located below the line GI exhibits WCF micro-combustibility (the combustion speed of the WCF composition is 10cm/s or less) according to ASHRAE standards.
Further, it is determined based on these results that: in the above 3-component composition diagram, the mixed refrigerant having the coordinates (x, y, z) at a composition lower than the line connecting points J, P ', Q, S', N, N ', M' and M exhibits microcombustibility according to ASHRAE standard (2L-stage (combustion speed of WCF composition and WCFF composition is 10cm/s or less)).
The GWP of each refrigerant mixture was evaluated based on the GWP of each refrigerant constituting the refrigerant mixture. The GWP of each refrigerant is based on the IPCC (Intergovernmental Panel on CLIMATE CHANGE; inter-government climate change specialization committee) 4 th report value. The GWP of HFO-1132 (E) is not described in this report, but is assumed to be 1 according to HFO-1132a (gwp=1 or less) and HFO-1123 (gwp=0.3; described in patent document 1).
The refrigerating capacity of each mixed refrigerant was obtained by using the fluid thermodynamic and transport property database (REFERENCE FLUID THERMODYNAMIC AND TRANSPORT PROPERTIES DATABASE (Refprop 9.0)) of the national institute of science and technology (National Institute of SCIENCE AND Technology (NIST)), and by performing theoretical calculation of the refrigerating cycle of the mixed refrigerant under the following conditions.
Evaporating temperature 5 DEG C
Condensing temperature 45 DEG C
Overheat temperature 5K
Supercooling temperature 5K
Compressor efficiency 70%
Based on these results, coefficient of performance (COP) was obtained by the following equation.
Cop= (refrigerating capacity or heating capacity)/consumed electric quantity
Further, regarding the freezing capacity and COP, the ratio with respect to R410A is shown.
With respect to the discharge pressure, the ratio with respect to R410A is shown.
These results are shown in tables 3 to 6, respectively.
TABLE 3
TABLE 4
TABLE 5
TABLE 6
Based on these results, it was judged that: in the case of the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total thereof are x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern enclosed by the lines AA1, A1B, BD, DR, RC, CO and OA respectively connecting the following 7 points or on the above lines (wherein the points on the lines BD, CO and OA are not included),
Point A (76.2,0.0,23.8),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0),
Lines AA1, A1B, BD, CO and OA are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on the line RC is represented by (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511), in which case the freezing capacity ratio based on R410A is 85% or more and the COP ratio based on R410A is 92.5% or more. The curve DR is obtained by the least square method from points D, R 'and 3 points R, and the curve RC is obtained by the least square method from points R, C' and 3 points C, as shown in table 7.
TABLE 7
In addition, it is determined that: in the case of the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern enclosed by the lines GG1, G1A1, A1B, BD, DR, RC and CG respectively connecting the following 7 points or on the lines (wherein the points on the lines BD and CG are not included),
Point G (72.0,28.0,0.0),
Point G1 (72.0,3.3,24.7),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines GG1, G1A1, A1B, BD and CG are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The points on the line RC are represented by (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511), and in this case, the freezing capacity ratio based on R410A is 85% or more, the COP ratio based on R410A is 92.5% or more, and the WCF micro-combustibility (combustion speed of WCF composition is 10cm/s or less) is exhibited according to ASHRAE standards.
In addition, it is determined that: regarding the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total thereof are x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern enclosed by lines JQ, QN, NM, MA, A1B, BD, DR, RC and CJ respectively connecting the following 9 points or on the above lines (wherein the points on lines BD and CJ are not included),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4)
Point N (65.9,21.6,12.5)
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QN, NM, MA1, A1B, BD and CJ are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on the line RC is represented by (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511), and in this case, the freezing capacity ratio based on R410A is not only 85% or more, but also the COP ratio based on R410A is 92.5% or more, and the micro-combustibility (2L grade (combustion speed of WCF composition and WCFF composition: 10cm/s or less)) is exhibited in accordance with ASHRAE standards.
In addition, it is determined that: regarding the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total thereof are x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of the pattern enclosed by or on the lines JQ, QR, RC and CJ respectively connecting the following 4 points (wherein the points on the lines CJ are not included),
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QR and CJ are straight lines,
The point on the line RC is represented by (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511), in which case the freezing capacity ratio based on R410A is 85% or more, the COP ratio based on R410A is 92.5% or more, and the condensing temperature slip is 1 ℃ or less.
In addition, it is determined that: in the case of the mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in the 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of or on the graph surrounded by lines SN, NM, MA1, A1B, BF, FS1 and S1S respectively connecting the following 7 points,
Point S (64.6,26.0,9.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point F (0.0,71.7,28.3)
At point S1 (26.8,54.4,18.8),
Lines SN, NM, MA1, A1B and BF are straight lines,
Line FS1 is denoted as (x, 0.0041x 2-0.7562x+71.7,-0.0041x2 -0.2438x+28.3),
The line S1S is represented by (x, 0.00155x 2-0.8939x+77.236,-0.00155x2 -0.1061x+22.764), and in this case, not only the refrigerating capacity ratio based on R410A is 85% or more, but also the COP ratio based on R410A is 95% or more, and the discharge pressure ratio based on R410A is 102% or less. Here, as shown in table 8, the curve FS1 is obtained by the least square method from 3 points S1, S1', and F, and the curve S1S is obtained by the least square method from 3 points S1, S', and S.
TABLE 8
In addition, it is determined that: in the case of a mixed refrigerant of HFO-1132 (E), HFO-1123 and R1234ze (E), when the mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within the range of a pattern or on the line defined by straight lines P 'Q, QQ and Q1P' connecting the lower 3 points, respectively, in which case not only the freezing capacity ratio based on R410A is 85% or more, but also the COP ratio based on R410A is 95% or more, and the condensing temperature slip becomes 1 ℃ or less
Point P (55.4,42.7,1.9),
Point Q (62.1,34.5,3.4)
Point Q1 (52.8,43.5,3.7).
The mixed refrigerants of HFO-1132 (E), HFO-1123, and R1234ze (E) and HFO-1234yf were evaluated in the same manner, and the results are shown in tables 6 to 12. In the following, the value of R in each coordinate represents the ratio of R1234yf (0 < R < 1) in the case where the total of R1234yf and R1234ze (E) is 1 in the composition. In addition, the letters and numbers (e.g., A, A, etc.) of each coordinate refer to the coordinate corresponding to the coordinate represented by the same letter and number in the mixed refrigerant of HFO-1132 (E), HFO-1123, and R1234ze (E). That is, the evaluation results are the same between the two coordinates but only r is different.
TABLE 9
TABLE 10
TABLE 11
TABLE 12
TABLE 13
TABLE 14
TABLE 15
The coordinates of each point are expressed as a function of r. The actual results were obtained as follows. Further, the point N r is the ASHRAE micro-ignition limit, and the ratio of HFO-1132 (E) becomes the maximum point.
TABLE 16
TABLE 17
TABLE 18
TABLE 19
TABLE 20
TABLE 21
TABLE 22
TABLE 23
Symbol description
1: Sample chamber
2: High-speed digital video camera
3: Xenon lamp
4: Observation lens
5: Observation lens
6: Annular filter
Claims (17)
1. A refrigerant-containing composition characterized in that:
The refrigerant comprises trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123) and trans-1, 3-tetrafluoropropene (R1234 ze (E)),
In the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on a range of a pattern surrounded by lines AA1, A1B, BD, DR, RC, CO and OA respectively connecting the following 7 points, wherein the points on the lines BD, CO and OA are not included,
Point A (76.2,0.0,23.8),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0),
Lines AA1, A1B, BD, CO and OA are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted by (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511),
The total content of HFO-1123, HFO-1132 (E) and R1234ze in the entire refrigerant is 99.5 mass% or more.
2. The composition of claim 1, wherein:
In the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on a range of a pattern surrounded by lines GG1, G1A1, A1B, BD, DR, RC and CG respectively connecting 7 points below, wherein the points on the lines BD and CG are not included,
Point G (72.0,28.0,0.0),
Point G1 (72.0,3.3,24.7),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines GG1, G1A1, A1B, BD and CG are straight lines,
The points on line DR are denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x +
13.7 A) the representation is given,
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
3. The composition of claim 1, wherein:
In the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on a range of a figure surrounded by lines JQ, QN, NM, MA, A1B, BD, DR, RC and CJ, respectively, connecting the following 9 points, wherein the points on the lines BD and CJ are not included,
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point D (0.0,86.3,13.7),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QN, NM, MA1, A1B, BD and CJ are straight lines,
The point on line DR is denoted by (x, 0.0057x 2-0.7688x+86.3,-0.0057x2 -0.2312x+13.7),
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
4. The composition of claim 1, wherein:
in the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on a range of a pattern surrounded by lines JQ, QR, RC and CJ respectively connecting the following 4 points, wherein the points on the line CJ are not included,
Point J (47.1,52.9,0.0),
Point Q (62.1,34.5,3.4),
Point R (23.7,71.3,5.0)
Point C (32.9,67.1,0.0),
Lines JQ, QR and CJ are straight lines,
The point on line RC is denoted (x, 0.00945x 2-0.9915x+89.489,-0.00945x2 -0.0085x+10.511).
5. The composition of claim 1, wherein:
In the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on the range of a pattern surrounded by lines SN, NM, MA1, A1B, BF, FS1 and S1S respectively connecting the following 7 points,
Point S (64.6,26.0,9.4),
Point N (65.9,21.6,12.5),
Point M (61.9,11.9,26.2),
Point A1 (40.0,30.0,30.0),
Point B (0.0,68.8,31.2),
Point F (0.0,71.7,28.3)
At point S1 (26.8,54.4,18.8),
Lines SN, NM, MA1, A1B and BF are straight lines,
Line FS1 is denoted as (x, 0.0041x 2-0.7562x+71.7,-0.0041x2 -0.2438x+28.3),
Line S1S is denoted (x, 0.00155x 2-0.8939x+77.236,-0.00155x2 -0.1061x+22.764).
6. The composition of claim 1, wherein:
In the refrigerant, when mass% of HFO-1132 (E), HFO-1123 and R1234ze (E) based on the total of them is x, y and z, respectively, in a 3-component composition diagram in which the total of HFO-1132 (E), HFO-1123 and R1234ze (E) is 100 mass%, the coordinates (x, y, z) are within or on a range of a figure surrounded by straight lines P 'Q, QQ and Q1P' respectively connecting the following 3 points,
Point P (55.4,42.7,1.9),
Point Q (62.1,34.5,3.4)
Point Q1 (52.8,43.5,3.7).
7. A refrigerant-containing composition characterized in that:
the refrigerant comprises trans-1, 2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and trans-1, 3-tetrafluoropropene (R1234 ze (E)) and 2, 3-tetrafluoro-1-propene (R1234 yf),
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, the points of HFO-1132 (E) and R1234yf are 100 mass%, and the points of R1234ze (E) and R1234yf are 100 mass% as vertices, the coordinates (x, y, z') are within a range of or on a graph enclosed by a straight line ArA1r、A1rBr、BrDr、DrRr、RrC、CO and OA r connecting the following 7 points, respectively, wherein the points on B rDr, CO r and OA are not included,
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Point R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0),
Point C (32.9,67.1,0.0)
Point O (100.0,0.0,0.0),
The total content of HFO-1132 (E), HFO-1123, R1234ze (E) and R1234yf in the entire refrigerant is 99.5 mass% or more.
8. The composition of claim 7, wherein:
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, the point where HFO-1132 (E) is 100 mass%, the point where HFO-1123 is 100 mass%, and the point where the sum of R1234ze (E) and R1234yf is 100 mass% are vertices, the coordinates (x, y, z'):
At 0.53 r > 0, in or on a graph surrounded by straight lines GG1、G1rA1r、A1rBr、BrDr、DrRr、RrC and CG connecting 7 points below, respectively, wherein points on lines B rDr and CG are not included,
Point G (72.0,28.0,0.0),
Points G r(72.0,1.7734r2 +4.5133r+24.7, 28.0-y),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0),
At 1.0 > r > 0.53, lies within or on the graph enclosed by straight lines GI、IAr、ArA1r、A1rBr、BrDr、DrRr、RrC and CG connecting the following 8 points, respectively, wherein the points on lines IA r、BrDr and CG are not included,
Point G (72.0,28.0,0.0),
Point I (72.0,0.0,28.0),
Point A r(-1.6r2 -6.0r+76.2,0.0, 100.0-x),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
9. The composition of claim 7, wherein:
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, and in which, in a 3-component composition diagram in which, as vertices, the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of R1234ze (E) and R1234yf are 100 mass%, the coordinates (x, y, z') are within or on a graph enclosed by straight lines JQr、QrNr、NrMr、MrA1r、A1rBr、BrDr、DrRr、RrC and CJ connecting the following 9 points, respectively, the points on lines BD and CJ are not included,
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point D r(0.0,-1.8r2 -4.1r+86.3, 100.0-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
10. The composition of claim 7, wherein:
in a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, the coordinates (x, y, z') are within the range of or on a graph surrounded by straight lines JQ r、QrRr、Rr C and CJ, respectively, connecting the following 4 points, wherein the points on the line CJ are not included,
Point J (47.1,52.9,0.0),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y),
Points R r(-4.6r2-0.5r+23.7,100.0-x-z,4.0r2 +1.6r+5.0) and
Point C (32.9,67.1,0.0).
11. The composition of claim 7, wherein:
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the total of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the total of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, and in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of the total of R1234ze (E) and R1234yf is 100 mass%, the coordinates (x, y, z') are within a range of a graph enclosed by straight lines SrNr、NrMr、MrA1r、A1rBr、BrFr、FrS1r and S1 rSr connecting the following 7 points, respectively, or on the lines, wherein the points on B rFr are not included,
Point S r(1.4r2+1.3r+64.6,-0.8r2 -4.0r+26.0, 100.0-x-y),
Points N r(-0.2r2+2.9r+65.9,4.8r2 -10.2r+21.6, 100.0-x-y),
Point M r(100.0-y-z,1.0r2-7.5r+11.9,0.8r2 +6.0r+26.2),
Points A1 r(40.0,-0.4r2 -7.4r+30.0, 60.0-y),
Point B r(0.0,-1.0r2 -9.1r+68.8, 100.0-y),
Point F r(0.0,-2.6r2 -7.3r+71.7, 100.0-y) and
Point S r(100.0-y-z,-3.8r2-3.5r+54.4,0.2r2 +6.7r+18.8).
12. The composition of claim 7, wherein:
In a 3-component composition diagram in which, based on the sum of HFO-1132 (E), HFO-1123, and R1234ze (E) and R1234yf, the mass% of HFO-1132 (E) is x, the mass% of HFO-1123 is y, the mass% of the sum of R1234ze (E) and R1234yf is z ', and the ratio of R1234yf in the case where the sum of R1234yf and R1234ze (E) is 1 is R and 0 < R < 1, and in which the point of HFO-1132 (E) is 100 mass%, the point of HFO-1123 is 100 mass%, and the point of the sum of R1234ze (E) and R1234yf is 100 mass%, the coordinates (x, y, z') are within a range of a graph enclosed by straight lines P rQr、QrQ1r and Q1 rPr connecting the following 3 points, respectively, or on the lines,
Point P r(-0.2r2-0.5r+55.4,100.0-x-z,0.6r2 +0.7r+1.9),
Point Q r(2.6r2+1.3r+62.1,-5.8r2 -2.5r+34.5, 100.0-x-y) and
Point Q r(-2.4r2-0.8r+52.8,100.0-x-z,3.6r2 +0.8r+3.7).
13. The composition of any one of claims 1 to 12, wherein:
and refrigerating machine oil, and the composition is used as working fluid of a refrigerator.
14. The composition of any one of claims 1 to 12, wherein:
As an alternative refrigerant to R410A.
15. Use of a composition according to any one of claims 1 to 13 as a replacement refrigerant for R410A.
16. A freezer, characterized in that:
A composition according to any one of claims 1 to 13 as a working fluid.
17. A method of operating a refrigerator, comprising:
a step of circulating the composition according to any one of claims 1 to 13 as a working fluid in a refrigerator.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-114159 | 2019-06-19 | ||
| JP2019114159 | 2019-06-19 | ||
| PCT/JP2020/024157 WO2020256112A1 (en) | 2019-06-19 | 2020-06-19 | Composition containing refrigerant, use of same, refrigerator having same, and method for operating said refrigerator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113950519A CN113950519A (en) | 2022-01-18 |
| CN113950519B true CN113950519B (en) | 2024-06-11 |
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| CN202080043594.8A Active CN113950519B (en) | 2019-06-19 | 2020-06-19 | Refrigerant-containing composition, use thereof, refrigerator having the same, and method for operating the refrigerator |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20220098460A1 (en) |
| EP (1) | EP3988866A4 (en) |
| JP (1) | JP6897850B2 (en) |
| CN (1) | CN113950519B (en) |
| WO (1) | WO2020256112A1 (en) |
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| JP2022138148A (en) * | 2021-03-09 | 2022-09-22 | ダイキン工業株式会社 | Composition containing refrigerant, use of the same, refrigerator comprising the same, and method for operating the refrigerator |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015115252A1 (en) * | 2014-01-31 | 2015-08-06 | 旭硝子株式会社 | Working medium for heat cycle, composition for heat cycle system, and heat cycle system |
| WO2015125534A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
| WO2015186670A1 (en) * | 2014-06-06 | 2015-12-10 | 旭硝子株式会社 | Composition for heat cycle system and heat cycle system |
| CN106133110A (en) * | 2014-03-18 | 2016-11-16 | 旭硝子株式会社 | Working medium for heat cycle, heat circulating system compositions and heat circulating system |
| WO2018047816A1 (en) * | 2016-09-07 | 2018-03-15 | 旭硝子株式会社 | Working medium for thermal cycling, composition for thermal cycling system, and thermal cycling system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170135855A1 (en) * | 2015-05-21 | 2017-05-18 | Vitaheat Medical, Llc | Patient warming system |
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2020
- 2020-06-19 EP EP20827347.4A patent/EP3988866A4/en active Pending
- 2020-06-19 CN CN202080043594.8A patent/CN113950519B/en active Active
- 2020-06-19 WO PCT/JP2020/024157 patent/WO2020256112A1/en unknown
- 2020-06-19 JP JP2020105814A patent/JP6897850B2/en active Active
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2021
- 2021-12-14 US US17/550,223 patent/US20220098460A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015115252A1 (en) * | 2014-01-31 | 2015-08-06 | 旭硝子株式会社 | Working medium for heat cycle, composition for heat cycle system, and heat cycle system |
| CN106029821A (en) * | 2014-01-31 | 2016-10-12 | 旭硝子株式会社 | Working medium for heat cycle, composition for heat cycle system, and heat cycle system |
| WO2015125534A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
| CN106133110A (en) * | 2014-03-18 | 2016-11-16 | 旭硝子株式会社 | Working medium for heat cycle, heat circulating system compositions and heat circulating system |
| WO2015186670A1 (en) * | 2014-06-06 | 2015-12-10 | 旭硝子株式会社 | Composition for heat cycle system and heat cycle system |
| WO2018047816A1 (en) * | 2016-09-07 | 2018-03-15 | 旭硝子株式会社 | Working medium for thermal cycling, composition for thermal cycling system, and thermal cycling system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021001322A (en) | 2021-01-07 |
| US20220098460A1 (en) | 2022-03-31 |
| CN113950519A (en) | 2022-01-18 |
| EP3988866A1 (en) | 2022-04-27 |
| WO2020256112A1 (en) | 2020-12-24 |
| JP6897850B2 (en) | 2021-07-07 |
| EP3988866A4 (en) | 2023-09-13 |
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